Nitrogen-phosphorus composition



Patented June 17, 1958 perature below about 150 0., preferably between about 90-140 C. The oxygen content of the gas mixture 2,839,375 should not exceed about volume percent and is preferably held to between about 0.1 and about 2 volume NITROGEN'PHOSPHORUS C'IOMPOSITIGN 5 percent. The ammonia content should be at least about Curtis o. Christian, Anaheim, cans, assignor, mesne 5 volume p en n y be as high a 999 volume assignments, to Collier Carbon and Chemical Corpopercent. However, control of the reaction temperature ration, a corporation of California is facilitated if the ammonia content of the mixture is No Drawing. Application January 27, 1955 I held beiow about 50 volume percent and the remainder Serial No. 484,567

A particularly useful gas mixture consists of about 15 8 Claims. (CI. 71-32) percent of ammonia, about 1-2 volume percent of oxyand about 83459 volume percent of nitrogen. t

is essential that the reaction temperature be maintained This invention relates to a new composition of matbelow about 150 C., and suitable control thereof may ter and to a method of making the same, and in parconveniently be attached by controlling the temperaticular concerns a new chemical compound of unknown ture and/or the composition of the gas mixture. Acmolecular structure containing the elements nitrogen and cording to a preferred mode of operation the body of phosphorus. molten phosphorus is maintained at about 130 C. and

A number of attempts have been made to prepare the temp rature of the gas mixture at its point of entry plant nutrient compositions containing a high pioporinto the ieaction vessel is maintained at about 95 C tion of nitrogen and phosphorus by reacting phosphorus Since the ieaction is preferably effected by reacting the or phosphorus pentoxide with ammonia or mixtures of reactants at the surface of a body of molten or solid ammonia and oxygen. Prior to the present invention, phosphorus, the latter most efficiently should take the however, the compositions so prepared were either hyform of a thin film or layer so that maximum surface groscopic, seini-pyrophoric or noxious-smelling materials is exposed to the gas mixture. which were very unsatisfactory for use as fertilizers. The reaction between the phosphorus, ammonia and I have now found that a stable non-hygroscopic and oxygen at a r action temperature belowabout 150 C. odorless product containing an exceptionally high prom is accompanied by a copious evolution of white fumes portion of nitrogen and phosphorus may be prepared This rnlaaterial is passes directly to a heating Zone or b a u between h h o i and oven werein it is so jected to a tem erature above g n carried out as herei naftgr described. The produic t about 0 C-, pr ferably betWeen about :25" and about so prepared is well adapted to use as a fertilizer and for a Period of m tw n a ut 0:05 and may also be employed as an intermediate in the preparaabout 5 Seconds, Preferably between about 02 and a ut tion of new phosphorusand nitrogen-containing com- 1 second. The heat-treated product, which constitutes pounds. It takes the form of a gray, finely-divided an intermediate product of the process, is then withamorphous lid hi h melts at 295 298 C I i drawn frorn the heating zone and collected by electrohighly soluble in water to form clear solutions having a p l p i Z b g a ll j y-gl ii leg r l van'e em suci as are use in co ectin car on ac is iiegeiidiii g iipo ii th r zi c iib ii tempeii aiure en ip lo y ed Pmduct lakes the form of a flugfiy While amorphous in its preparation, but such analysis is characteristically Solid 0f Unknown Smlcturfb Which melts With p as follows: sition at 290-315 C. It is soluble only to a very lim- Percent b Wt, ited extent in water and common organic solvents but is Total nitrogen 2840 4,5 ly hy r lyze by aqueous alkah's and. acids. Char- Total phosphorus 28-30 510ml lly 1t 11 111 about 21 percent total nitrogen, Total hydrogen 6-6.5 about 31.8 P nt otal phosphorus, about 3.7 percent Oxygen (by difference) -4-0 t0181 hydrogen, and (by difference) about 43.5 percent oxygen.

The Hitmgen and phosllhorus analyses the P :6 The second stage of the present process is conveniently to 3011mm approxlmately 2 F 5 0f nltl'ogel} P carried out batch-wise simply by charging the product atom P p its Y dlfifacllfin P l Infraof the first stage and anhydrous liquid ammonia into red spesmlm and other analytical Properties {11010316 an autoclave or other pressure vessel and heating the lhls new Product to be P l/ 111 nature; but ITS I110- mixture to a reaction temperature above about C.

preferably between about C. and about 300 C and under autogenic pressure. During the reaction the its prearation rather than as a distinct Chemical eomautogenc pressure within the reaction vessel rises to a pound. maximum value which is usually between about and The new product is prepared by a two-stage process, about 500 p. s. i. g., depending upon the reaction temthe first of which involves rea ting el mental ph GO perature and ratio in which the reactants are employed. phorus wi h amm n a nd oxyg n at a relatively low Usually the reaction is completed in from about 1 to temperature after which the reaction product so formed about 20 hou s, depending upon the reaction temperais heat treated at a moderately elevated temperature for tore employed. The ammonia reactant is preferably a short period of time. The second stage of the process provided in relatively large excess, e. g., 5l0 pounds consists in reacting the heat-treated product of the first q: of anhydrous ammonia are usually employed per pound stage with anhydrous ammonia at an elevated temperaof the first-stage reaction product. true and under superatmospheric pressure Upon completion of the secondstage reaction, the Conveniently, the first stage of the process is carried reaction vessel and contents are cooled to atmospheric out by heating yellow elemental phosphorus to a temtemperature and any excess ammonia is vented from perature somewhat above its melting point, e. g., to m the vessel and recovered for re-use. The reaction prod- 50-l40 C., and passing a gas mixture comprising uct, which constitutes the new nitrogen-phosphorus comammonia and oxygen over the surface of the molten position of the invention, is recovered from the vessel phosphorus while maintaining the environmental ternas a gray solid which differs markedly from the first-stage gray powder which that it is completely soluble in water.

reaction product in be purified by fractional crystalliza- If desired, it may As will be apparent to those skilled in the art, various engineering and manipulative techniques may be applied in preparing the new product. Both stages of the process by which it is prepared may be carried out batchwise, semi-continuously or continuously, and various methods of achieving the proper temperatures and control of the same may be employed. In essence the invention consistsin the process of reacting elemental phosphorus with oxygen and ammonia at a reaction temperature below about 150 C., followed by heating the product so formed to a temperature above about 300 C. and thereafter reacting the heat-treated product with anhydrous ammonia at a temperature above about 50 C. under superatmospheric pressure. It also consists in the novel product obtained by such process.

The following example will illustrate one way in which the principle of the invention has been applied but is not to be construed as limiting the same:

Example A gas mixture consisting of 11.6 volume percent of ammonia, 1.4 volume percent of oxygen, and 87.0 volume percent of nitrogen was heated to a temperature of about 95 C. and passed through a tubular reaction chamber which comprised, in succession, a horizontal reaction zone which was maintained at a temperature of about 130 C., a horizontal heat-treating zone which was maintained at a temperature of about 425 C. and a vertical product-collection zone containing an electrostatic precipitator. A body of molten yellow phosphorus was maintained in the reaction zone. As the gas mixture swept across the surface of the body of phosphorus, copious white fumes were evolved and were carried by the gas stream through the heat-treating zone and across the electrostatic precipitator. The rate of gas flow was such that the white fumes had a residence time within the heat-treating zone of about 0.5 second. The product which was precipitated from the gas stream as it passed through the product-collection zone was a very finely-divided fluffy white powder having the analysis and properties previously given for the first stage reaction product.

were charged to a pressure vessel at a temperature of about 110 C. During the heating the maximum pressure developed within the vessel was about 410 p. s. i. g. At the end of the heating period the vessel and contents were cooled to room temperature, the ammonia was vented from the vessel, and the product was withdrawn as a was completely soluble in water. It contained about 28 percent nitrogen and about 28 percent of phosphorus, corresponding to the fertilizer designation 2826410.

in employing the new product as a fertilizer or plant nutrient it may conveniently be applied to the soil and/or plants in the form of an aqueous solution. Since the product is exceptionally rich in nitrogen and phosphorus (containing plant nutrient elements to an extent of better than 90 percent) it is eifective in relatively small quantities, and aqueous solutions of the same having excellent plant nutrient value may be relatively dilute, e. g., they may contain as little as 0.1- percent of the active ingredient. The new product may also be employed in solid form as by direct application to the surface of the soil or admixture therewith by harrowing or the like.

Other modes of applying the principles of my invention may be employed instead of those explained, change for about 18 hours.

being made as regards the materials or methods employed provided the steps or product stated by any of the following claims, or the equivalent of such stated steps or product, be employed or obtained.

1, therefore, particularly point out and distinctly claim as my invention:

1. The process which comprises (1) contacting elemental phosphorus wi'h a gas mixture comprising be tween about 0.1 and about 5 volume percent of oxygen and at least about 5 volume percent of ammonia at a reaction temperature below about 150 C., (2) subjecting the reaction product so obtained to a temperature above about 300 C. for a period of time between about 0.05 and about 5 seconds, and (3) heating the product of step (2) with anhydrous ammonia at a reaction temperature above about 50 C. and under autogenic pressure for a period of time suflicient to efiect the formation of a water-solublev amorphous solid having a total nitrogen content of about 28-30 percent by weight and a total phosphorus content of about 2830 percent by weight.

2. The process of claim 1 wherein, in step (1), the gas mixture consists of between about 0.1 and about 5 volume percent of oxygen, between 5 and about 50 volume percent of ammonia, and the remainder is a gas which is non-reactive at the said reaction temperatures.

3. The process of claim 1 wherein, in step (1), the gas mixture consists of between about 1 and about 2 volume percent of oxygen, between about 5 and about 15 volume percent of ammonia, and between about 83 and about 89 volume percent of nitrogen.

4. The process of claim 1 wherein, in step (1), the said reaction temperature is between about 90 C. and about 140 C.

5. The process of claim 1 wherein, in step (2), the temperature is between about 425 C. and about 600 C. and the time of heating is between about 0.2 and about 1 second.

6. The process of claim 1 wherein, in step (3), the temperature is between about C. and about 300 C.

7. The process of claim 1 wherein, in step (3), between about 5 and about 10 parts by weight of anhydrous ammonia are employed per part by weight of the product formed in step (2).

8. The process which comprises (1) passing a gas mixture comprising between about 0.1 and about 5 volume percent of oxygen and at least about 5 volume percent of ammonia over the surface of a body of molten yellow phosphorus while maintaining an environmental temperature between about 90 C. and about C. whereby white fumes are evolved from said surface, (2) carrying said fumes through a heating zone where they are subjected to a temperature between about 425 C. and about 600 C. for a period of time between about 0.05 and about 5 seconds and collecting the product so formed, and (3) heating the product formed in step (2) with between about 5 and about 8 parts by weight of anhydrous ammonia at a temperature between about 100 C. and about 300 C. and under autogenic pressure for from about 1 to about 20 hours whereby there is obtained a water-soluble amorphorus solid having a total nitrogen content of about 28-30 percent by weight and a total phosphorus content of about 28-30 percent by weight.

References Cited in the file of this patent UNITED STATES PATENTS 

1. THE PROCESS WHICH COMPRISES (1) CONTACTING ELEMENTAL PHOSPHORUS WITH A GAS MIXTURE COMPRISING BE TWEEN ABOUT 0.1 AND ABOUT 5 VOLUME PERCENT OF OXYGEN AND AT LEAST ABOUT 5 VOLUME PERCENTOF AMMONIA AT A REACTION TEMPERATURE BELOW ABOUT 150*C., (2) SUBJECTING THE REACTION PRODUCT SO OBTAINED TO A TEMPERATURE ABOVE ABOUT 300*C. FOR A PERIOD OF TIME BETWEEN ABOUT 0.05 AND ABOUT 5 SECONDS, AND (3) HEATING THE PRODUCT OF STEP (2) AWITH ANHYDROUS AMMONIA AT A REACTION TEMPERATURE ABOVE ABOUT 50*C. AND UNDER AUTOGENIC PRESSURE FOR A PERIOD OF THE TIME SUFFICIENT TO EFFECT THE FORMATION OF A WATER-SOLUBLE AMORPHOUS SOLID HAVING A TOTAL NITROGEN CONTENT OF ABOUT 28-30 PERCENT BY WEIGHT AND A TOTAL PHOSPHORUS CONTENT OF ABOUT 28-30 PERCENT BY WEIGHT. 